MOVEMENT AND ACCUMULATION OF APPLIED COPPER IN A HARDWATER SOUTHEASTERN MICHIGAN RESERVOIR Thesis for the Degree of M. S. MICHIGAN STATE UNIVERSITY Kenneth Ray Roberts 1966 _—_ IIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIQOIIIIIIIIIZIIIIIII L131: R . A Y 3 1293 10444 Michigan State University HESIS ABSTRACT MOVEMENT AND ACCUMULATION OF APPLIED COPPER IN A HARDWATER SOUTHEASTERN MICHIGAN RESERVOIR by Kenneth Ray Roberts A study was made from January through May, 1965 on the dynamics of applied copper movement and accumulation in 85-acre Adrian Lake, a southeastern Michigan hard water water supply reservoir. The lake has accrued a copper accumulation during more than ten years of intensive algal control with copper sulfate. During the study the lake's water dynamics were found to be con- stantly changing. Analysis of lake water copper profiles resulted in the conclusion that water movement is a very significant factor in the distribution of applied copper. Conditions apparently most important in the mechanism are volume of lake inflow, the rate of c0pper sulfate enter- ing the system, and water volume going over the dam and/or through the sluices. Copper is transported out of Adrian Lake both by direct flow from the constant-flow source and from the sediments themselves. In each instance water current is the vehicle which determines the rate of removal. Total copper values in the sediments were found to be high. A maximum downlake value of 1,982 ppm. was found two cm. deep at a point 1,145 feet from the point of copper sulfate introduction. Copper con- tent progressively decreased with increasing sediment depth. This ver- tical trend apparently reflects the lake's rate of copper sulfate appli- cation. 'he data were considered insufficient to accept or reject the hypothesis of increasing sediment copper concentrations with increasiné water depth in Adrian Lake. Nor did the data provide evidence of a Kenneth Ray Roberts strong relationship between sediment copper content and distance down lake from the constant-flow device. Wave action and intensified inflow, whenever they might occur, are attributed to result in continual full or partial downlake re-distribution of these compounds. A literature review resulted in the conclusion that the high af- finity of organic matter for copper ions has gone generally unrecognized in the field of lake copper ecoloay. A thoroush understanding of react- ions of copper ions in natural waters is precluded until such a time when a more ample backbround is established on the form of the copper ion lake water, the organic and inorganic materials present, their inter-relations, and relative copper affinities. MOVEMENT AND ACCUMULATION OF APPLIED COPPER IN A HARDWATER SOUIHEASIERN MICHIGAN RESERVOIR By Kenneth Ray Roberts A THESIS Submitted to Michigan State University in partial fulfillment of the requirements for the degree of MASTER OF SCIENCE Department of Fisheries and Wildlife 1966 ACKNOWLEDGEMENTS I wish to acknowledge the patient guidance and advice supplied to this project by my advisor, Dr. Eugene Roelofs and the advice and assistance of Drs. Peter Tack, Andrew Timnick and Robert Ball. I am especially indebted to Messr's Carl Nelson and Garnet Campbell of the Adrian City Water Department for the great amount of time and assistance provided in collection of field data and provision of background informa- tion and to the Michigan State Agricultural Research Station for financial assistance provided. My thanks go also to the Michigan Water Resources Commission for the welcome use of its power ice auger and to Mr. Carlos Fetterolf for the insight he provided on Michigan lakes and streams. Use of the Ohlmacher-Gleason coring prototype was graciously made pos- sible by Dr. Dale Gleason, presently of the Sault Ste. Marie Branch of Michigan Technological University. The Fish Section of the Michigan De- partment of Conservation made existing Adrian Lake survey data available. Fellow graduate students Willard Gross and Al Jensen provided both field and taxonomic assistance in the fishery survey of Adrian Lake. Finally, I wish to acknowledge the encouragement and assistance provided by my wife, Judith, without whom the project might never have been undertaken. ii TABLE OF CONTENTS ACKNOWLEDGEMENTS LIST OF TABLES LIST OF FIGURES INTRODUCTION . . . . . . . . . Literature Review . . THE STUDY AREA: ADRIAN LAKE Location Drainage Area Geology and Soil Types Erosion Water Quality . . . . . . . . . . . Adrian Lake Proper The Fish Population . . . . . . . . . . . . METHODS I. II. COLLECTION AND PROCESSING OF WATER SAMPLES Lakewater Fractions Processing of Total Copper Fractions Processing of Sestonic Copper Fraction Processing of Filtrate Copper Fraction Measurement of Ionic Copper SAMPLING SEDIMENT FOR COPPER Selection of Sampling Stations Ohlmacher-Gleason Frozen Coring Device Miscellaneous Core Collection iii Page ii vi vii 10 10 13 19 19 20 21 21 21 22 22 22 24 26 III. IV. COPPEAi ANALYSIS 0 O O O O O O O O O O O O 0 Procedure for Determination of Copper in Lake Water . . . Procedure for Determination of Copper in Sediment . . . SUPPLEMENTARY DATA . . . . . . . . . . . . Copper Sulfate Application Data . . . . . . Lake Discharge and Water Plant Consumption Data Water Plant Consumption . . . . . . . . . . General Water Chemistry Measurements . . . RESULTS AND DISCUSSION . . . . . . . . . . . . . . . . I. II. III. S UMI‘IA R Y ADRIAN LAKE DURING THE STUDY . . . . . . . H-ion Concentration . . . . . . . . . . . . Dissolved Oxygen During Under-ice Sampling Dissolved Oxygen During Open-Water Sampling Alkalinity . . . . . . . . . . . . . . . . MOVEMENT OF APPLIED COPPER IN THE LAKE . . The Constant-Flow Copper Sulfate Device and its Operation Reliability of Lake Water Copper Analyses . . . . . . . . Water Movement and Its Effect on Lake Water Copper . . . Effect of Copper Sulfate on Lake Water Copper . Estimated Amount of Copper Carried out of the Lake . . . DISTRIBUTION OF APPLIED COPPER IN THE SEDIMENTS History and Mode of Copper Applications . . Reliability of Sediment Copper Analyses . . Find ings O O O O 0 O O O O O O O O O O O O LI'AEMTURE CITED 0 O O O 0 O O C O 0 O O O O O O O C 0 iv 30 31 31 31 33 33 35 35 35 35 36 36 36 36 37 38 44 46 43 48 49 50 56 60 Page APPED‘VDIXES O O O O O 0 O O O O O O O O O O 0 Appendix 1. Dissolved oxygen and pH values recorded at Adrian Lake, 1965 . . . . . . . . . . . . 63 Appendix 2. Alkalinity values recorded at Adrian Lake, 1965 O O O O O O O O O O O O O O C O O 64 Appendix 3. Lakewater copper values recorded at Adrian Lake, 1965 (Cu expressed as mg/liter). . . . 65 Appendix 4. Sediment core copper values recorded at Adrian Lake, 1965 O I O O O O O O O O O O O 68 v Table Table Table Table Table 1. 20 3. 4. LIST OF TABLES Results of the Adrian Lake Seining-gill net Survey conducted on June 14 and 30, 1965 Summarization of fish population information on Adrian Lake Stocking record for Adrian Lake as obtained from the Michigan Department of Conservation Summarization of estimates for pounds of applied copper discharged from Adrian Lake during the period April 14 through June 4, 1965 Pounds of copper sulfate applied to Adrian Lake over the period 1951-64 . vi Page 15 16 17 47 48 Figure Figure Figure Figure Figure Figure Figure Figure LIST OF FIGURES A map of the study site, Adrian Lake, showing water sampling stations and the study areas A, B, and C. A map of the study site, Adrian Lake, showing the sampling distribution of the twenty-eight sample cores . . . . . . . . . . . . . . Position and action in sediment of the Ohlmacher- Gleason frozen corer, as reproduced from Figure 4 of Ohlmacher's thesis Analyses of two separate series of 100 ml water samples from the April 14 collection for total copper, illustrating the precision of the batho- cuproine method for copper analysis . . . . . . Comparison of total copper concentration and lake water resistance data for March 15, 1965, which illustrates the effect of a density current on copper concentration . . . . . . . . . . . . A diagram illustrating six vertical profiles of total copper taken at Station III in relation to sluice gate openings, Cu804 introduction, and ice cover . . . . . . Vertical profiles of total copper in mg. per k0. dry sediment from six Adrian Lake cores A graphic presentation of Adrian Lake sediment core copper concentration with respect to distance from the point of copper sulfate introduction vii Page 23 25 39 4O 42 51 54 INTRODUCTION Copper compounds, primarily copper sulfate (Cu804.5H20), but in- cluding copper carbonate and copper oxide, have been widely applied to water areas for varying reasons. The most common use is for algal and bacterial control in water supplies. Other uses include the control of leeches, higher aquatic plants, fish diseases, and snails (for swimmers' itch). At least two state conservation agencies (Massachusetts and Ohio) apply copper sulfate to lakes routinely to stimulate fish movement, and thus increase the catch of fish in survey nets (Tompkins and Bridges, 1955; Brown, 1964). Sustained annual prOgrams of copper sulfate application carried out over long periods are not uncommon. Lakes Menona, Waubesa, and Kegonsa of the Madison Lakes, Wisconsin have received large applications of copper Sulfate annually for a period of at least nineteen years for algal control. As part of a swimmers’ itch program, Houghton Lake in Michigan received 555,400 pounds of copper sulfate from 1944 to 1963. As part of the same prOgram over the same interval, Michigan's Big and Little Glen Lakes received 104,900 pounds.1 Documentation of the more immediate toxicity of copper applica- tions on aquatic fauna is fairly extensive. However, the question of po- tential long range negative effects of repeated copper applications on lake ecosystems is meagerly treated in the literature, despite the fact lFetterolf, Carlos. 1963. Comments on the use of copper sulfate and the effects on lake ecology. Michigan Water Resources Commission mimeographed report. 2 that widespread speculation on this matter does exist. Hasler (1949) ex- pressed concern by writing, ”The question is not how little can be used to avoid killing fish, but what will be the effect of accumulations of copper in lake muds....” Hasler cited Frey (1940) who maintained reduc- tion of the aquatic vegetation and molluscan fauna of lakes Menona, Waubesa, and Kegonsa occurred with the addition of copper. Klein (1957) and Placak et a1. (1950) report that as little as 0.01 ppm. copper has a marked depressing effect on the B.O.D. of sewage. Rudgal (1946) found that increasing copper concentration in sludge caused a decreasing rate of digestion. Although 2,500 ppm. had a negligible effect, 50,000 ppm. allowed only 5 percent of normal gas production. Equally meager evidence exists which suggests that high copper concentrations accumulated in the sediments does not harm aquatic ecology. Mackenthun and Cooley (1952) produced laboratory evidence that the copper accumulation then present in Lake Menona sediments (as high as 480 ppm.) was not toxic to Pisidium sp. over a 60—day period. They also reported that extreme concentrations (9,600 ppm.) were needed to kill certain bot- tom dwelling organisms from Lake Mendota. Domogalla (1935) reported that, "rooted aquatics grew luxuriantly through all eleven years of copper sul- fate treatment at Lake Menona." Tompkins and Bridges (1958) reported that Lake Quannopowitt, Massachusetts, despite a long history of copper application displayed above average net catches of fish for that state. Moyle (1949) pointed out that commercial fishing yields were higher for a group of four Minnesota lakes treated with copper sulfate over a twen- ty-four year period than for five adjacent untreated lakes. Obviously, any substance as toxic as copper introduced in suffic- ient quantities will influence lake ecolOgy. The question of whether changes caused by accumulations of this heavy metal are of kind and sig- nificance to warrant concern cannot be answered until many more data are available. The general objective of the present study was to measure the dy- namics of movement and accumulation of copper in a lake receiving annual applications. Specific objectives of the study were: (1) measurement of the distribution of accumulated copper in the sediments of a treated hard- water lake with respect to depth and distance from the point of copper sul- fate introduction; and (2) periodic analyses of water profiles during the 1964-65 winter and 1965 Spring to record vertical concentrations of cop- per, dissolved oxygen, and pH in a hardwater lake during these periods. The water profile data were supplemented with lake discharge estimates to enable a projection of the amount of applied copper (regenerated from the sediments or otherwise) that was carried out of the lake by spring dis- charge. Adrian Lake at Adrian in southeastern Michigan was the site of data collection. It has accrued copper during more than ten years of algal control with copper sulfate by the City of Adrian. This hardwater, 85-acre, gourd-shaped reservoir was an excellent study site, because of its small size, relatively unpolluted state, and the mode of copper sul- fate application. Most of the chemical is introduced by a constant-flow device located at the lake's stream inlet, although additional treatments are made by boat. The stationary source of introduction provided a unique oppontunity to measure copper accumulation in the sediments of a hardwater lake with reSpect to (1) distance from the point of copper sulfate intro- duction and (2) water depth. Literature Review Little is known about mechanisms of copper ion reactions in natural waters. Copper ions react readily with many materials common at one time or another to lakewater. These substances include both organic matter (algae, higher aquatic plants, invertebrates, organic colloids, vertebrates, etc.) and inorganic matter (carbonates, chlorides, clays, hydroxides, oxygen, etc.). It seems universally accepted that most applied copper finds its way to the bottom, although this may not necessarily be true. Several mechanisms for its course to the bottom have been advanced. As early as 1930, precipitation of copper salts after applications to hardwater west- ern lakes was observed (Hale, 1954). Prytherch (1934) suggested that wastes of an alkaline character may cause precipitation of normal amounts of copper from river water. Prescott (1948) and Nichols et al. (1946) experimentally confirmed that precipitation of a bluish substance does occur from water with pH above neutral. Nichols et a1. feel that, ” . . . much of the copper added to lake waters of notable alkalinity is precipi- tated as a basic copper compound, of somewhat variable composition, de- pending upon prevailing conditions . . ." Hutchinson (1957) points out that two well-defined basic copper carbonates (malachite and azurite) are known in nature and the mechanism of basic copper carbonate formation is likely to be complicated. Riley (1939) in work on softwater Connecticut lakes cited evidence which indicates binding with algae and colloidal organic matter is a prime means of copper deposition. Benoit (1956) reported that Riley later de- termined that copper added to Lindsley Pond inlet water was rapidly fixed and that the copper was not precipitated through formation of insoluble hydroxide, carbonate, phosphate, or sulphide. It might be noted that the concept of alkaline water precipitat- ing all applied copper is presently widely held, yet is based on very limited evidence. Hutchinson cites unpublished data collected by Stecker in 1938, which compares total copper concentrations of more alkaline to softwater Wisconsin lakes. Based on measurements from 136 lakes, the data actually indicate a slightly higher copper concentration in the more alkaline lakes (32 mg. m’3) than in the softer lakes (29 mg. m'3). Hutch- inson attributed these results to a tendency for water with more total solids in solution to contain more c0pper and came to the conclusion that Stecker's data gave no indication of copper content of harder waters with natural concentrations being regulated by precipitation. A possibly important facet of copper ecology heretofore little considered in the literature is the importance of dissolved organic mate- rials such as amino acids, porphyrins, and carboxylic acids in tying up copper in lake water. Although limited information presently exists on the dissolved organic fraction of fresh waters, work by Shapiro (1959) shows the existence of a mixture of hydroxy carboxylic acids in softwater Connecticut lakes. Vallentyne (1957) indicated the occurrence of amino acids, polypeptides, and porphyrins in natural waters. FOgg and Westlake (1955) reported that an extracellular polypeptide produced by Anabaena s2. formed a soluble complex with various ions including copper. Saunders (1957) suggested that dissolved organic substances, acting as chelators, may influence concentration of trace elements in natural waters. The high affinity of organic matter for copper ions is widely rec- ognized and documented. Soil scientists have been particularly interested in copper exchange capacity of the soil organic fraction. Bremmer, et a1. (1946), Coleman, et a1. (1956), and Broadbent (1955) all report the exist- ence of stable complexes between soil organic matter and copper. Broad- bent and Oh (1957) reported that soil organic matter complexes were found capable of forming complexes with copper in very dilute solution, and the amount of complex formed was shown to be dependent on copper concentra- tion, pH, and time of contact. Thompson (1950), working on browning re- actions of foods, calls proteins avaricious copper-grabbers; he reports that a neutral solution of protein, such as casein or albumen, will satur- ate iteslf with copper while in contact with an insoluble copper compound, such as the oxide, in a relatively short time. Corwin (1950) reports that amino acids will break copper-ammonia complexes to take the copper and that the affinity of porphyrins for copper is so great that they will ex- tract it from copper sulfide. Assuming the constant presence of dis- solved (and particulate) organics in both hard and soft water, it seems that ionic and/or inorganically bound copper would eventually find its way into the ”avaricious” organic matter. Obviously, a thorough understanding of copper ion reactions in natural waters is precluded until an ample background is established on the form of copper ion in the water, the organic and inorganic materials present, their inter-relationships, and relative affinities for copper. THE SlUDY AREA: ADRIAN LAKE Location Adrian Lake (Figure 1) lies within Sections 26 and 35 of Township 6-3 Range 3-E, Lenawee County, Michigan. It is located on the northwest side and within the corporation limits of the City of Adrian. This 35.5- acre reservoir lies on Wolf Creek. Drainage Area Wolf Creek is part of the Raisin River Drainage. It flows direct- ly into the Raisin River, which in turn flows into Lake Erie. he land area draining into Adrian Lake itself is approximately 80 square miles.2 The headwaters of Wolf Creek arise in a series of small lakes in Cambridge and Franklin townships of Lenawee County. The connecting ditches between the lakes are intermittent, draining into Wolf Creek only during periods of high water. Wolf Creek itself is not intermittent and receives water from several tributaries, including Hunt, Ryan, Pouty, Onsted, and Black Creeks. Early settlers found Lenawee County to be covered with dense for- ests. Red, white, and black oaks, sugar maples, and beech were the prin- ciple species. Little or no virgin timber remains. Presently existing woodlots are small and largely pastured (Striker and Harmon, 1961). Wolf Creek's watershed consists primarily of farmland. It does include the very small rural towns of Onsted and Springville. The 1954 census showed the average Lenawee County farm to be 123 acres with major 2Michigan Department of Conservation Map of Lenawee County Z .I p. P P323; 8%; 10' ' .90 Site of pipe feeding 4,70 CuSO4 into lake. $0 .0 Sampling station 0 located one mile upstream at the Tipton Hwy. bridge. 0 water sampling station 0 I 600’ 1200' I 85. 5 acres / Lenawee County T. 68 R. 3E Sect. 23, 25 AREA c 1 \\ .6 f, plant intake * 20' i \ water 20' plant m ‘ V outflow A map of the study site, Adrian Lake, showing water sampling stations and the study areas A, B, and C. “\ Figure l. sources of income listed as field crops, dairy, livestock, poultry and fruit, in that order. Primary field crops include corn, oats, wheat, soybeans, hay and sugar beets (Striker et al.). GeolOgy and Soil Types Bedrock formations underlying Lenawee County are flat-lying sedi- mentary rocks. Glacial action ground up the bedrock and left deposits of drift. Thus, the surface features of the watershed are a reflection of the glacial action. Wolf Creek's drainage area is comprized of three general soil as- sociations (Striker et al.). The northern-most portion in the headwaters consist of rolling to hilly, well-drained loamy sands. The central part is nearly level, consisting of imperfectly and poorly drained soils de- veloped from clay loams, silty clay loams and clays. The lower portion diSplays undulating and rolling soils developed from limy clay loans, silty clay loams and clays. More Specifically, a large portion of Wolf Creek bottomlands, in- cluding the site of Adrian Lake, are of the Genessee and Griffin loam series. Gennessee soils are well drained and consist of an alluvium made up of loam, sandy loam and silt loam. Griffin soils are found in swales and old stream channels, are subject to overflow, and receive fresh de- posits when flooded. Most Griffin areas are narrow and less than three acres in size. In Lenawee County, they are found in such intricate mix- tures with the Genessee Series that the two are mapped together. These soils are fairly fertile and easy to till (Striker et al.). Erosion During periods of higher water, Wolf Creek and Adrian Lake become visably muddy. Striker et al. report that both of the upper watershed's 10 soil associations require special land management practices to control erosion. An outstanding example of watershed erosion was observed by the writer during the study. On February 10, 1965 Adrian City water person- nel made an entry in the water plant diary which reads, ”high water and mud,” following a runoff from thawing snow. During late February and early March, sediment cores were collected through the ice. Examination of these cores showed a contrasting brown layer of fresh sediment one- eighth to three-eighths inch thick on the surface phase of each black core. This sediment was apparently deposited in the lake during and after the runoff. Water Quality The Adrian Lake drainage discharges a moderately hard enriched water. Bicarbonate alkalinity ranges from 150-350 ppm. The enrichment is sufficient to cause problem algal blooms in the lake with great fre- quency. As early as 1946, the Adrian Water Board chemist treated the lake with copper sulfate to control these blooms.3 Adrian Lake Proper Adrian Lake displays characteristics common to most stream im- poundments, including a shallow upstream end, and gradual deepening to the deepest point of 21 feet near the dam. Soundings show that much of the impounded stream channel is still intact. The lake is gourd-shaped, and the shoreline is far from regular. 31946 Adrian Lake Survey, Institute for Fishery Research, Michigan Department of Conservation. August 20, 1946. 11 The dam. The dam was constructed in 1941, and filling occurred in 1942. Approximately 600 feet wide and 30 feet tall, it is comprised of earthen fill, which is protected from wave action by stone riprap on the water side. At the extreme south side a concrete spillway, complete with two 42 X 42-inch sluices, was constructed. Lake outflow occurs at this point. The concrete dam is 25 feet high, and the spillway is 66 feet wide. The center 9-foot 4-inch spillway section is two and one-eighth inches lower than the remaining, forming a low flow weir. The entire Spillway is adapted to receive 12-inch high oak planks, which are install- ed when additional water storage is desired. The water plant draws raw water for municipal use from an intake located on the north end of the dam. The intake is approximately 5 feet underwater. Water level fluctuation. In addition to seasonal fluctuations, Adrian Lake is subject to certain drawdowns, which are considered condu- cive to water plant operations and municipal water consumption. Installation of 12-inch planks at the Spillway occurs each spring. In 1965, installation of the planks with the sluice gates closed brought the water level up one foot in five days. The sluice gates are an important cause of fluctuation. The 42 X 42-inch gates are capable of draining 576 million gallons per day when wide open. In practice they are seldom open more than six inches, and then only for short periods. Even this partial opening has a signifi- cant effect on lake level at times. Dry conditions over the past few years have resulted in low lake levels. In 1963 and 1964, spring rains were sufficient to fill the lake, 12 but permitted little or no overflow. During this period, the sluice gates were never opened. The lake bottom. The lake bottom is essentially a reflection of the original stream valley. Bottom slope is varied, being generally low at the upper end and increasing as the dam is approached. The stream channel still exists, and there is evidence which shows it is still functional when the sluice gates are open. Bottom materials consist primarily of rubble, gravel, sand, silt, clay and organic detritus. The dam riprap contains numerous boulders. The gravel and sand beds are found almost exclusively on wave-washed areas, particularly at the areas exposed to north-wind wave action. The deeper and less exposed bottom areas consist of silt-clay deposits. The deepest area, which is near the dam, exhibits a black-organic clay bottom. Organ- ic matter is not present in abundance, because air-drying of this black clay material yields the characteristic color of grey clay. Numerous stumps from trees cut prior to inundation are present, especially in Area A. Adrian Lake inadvertently serves as a stilling basin for Wolf Creek. The result is that remaining original Genessee and Griffin soil series of the lake bed are being covered by erosion materials from the watershed. These foreign materials include gravel, sand, silt, clay and organic detritus. In addition, organic matter is contributed by meager beds of Potamogeton natans, P. pectinatus, and Najas sp., which are found in limited patches. Lake margin characteristics. The shoreline slope is a reflection of the original impounded area. The slope is moderately low at the upper 13 end. The lower half of the lake has very little shallow water due to the dam and high banks, which drop rapidly to the old valley bottom. Erosion is conspicuous in many places. The higher banks in all places have been gradually undercut because of their steep slope. Have erosion, however, is not proceeding at a rapid rate. Zones of submerged higher aquatic vegetation are historically few in the lake and are restricted to sheltered areas. Carbine and Cooper4 in August, 1946 reported, ”silty water made good cover, vegetation scant.” C. M. Taube5 in June and September, 1953 reported, ”. . . virtually no vegetation; Najas 22,, Potamogeton §p. observed at the Girl Scout Camp and south.” At the time of the current work, only 2. natans, P. pectinatus, and Naj§§_§p. were observed, and then only in scant, isolated beds. Actually, shore holding capacity due to submerged higher aquatic vegetation is minimized by this lack of development. During the early 1964-65 winter, the water level was about two feet below dam-top level, exposing a two to ten-foot-wide strip of lake bottom to the snow and air. The effect of such fluctuation on higher aquatic vegetation development can only be conjectured. The Fish Population Survey_history. Since filling in 1942, Adrian Lake has received three fish surveys by biologists of the Michigan Institute For Fisheries Research. The first occurred in 1946 and was made by G. P. Cooper and W. F. Carbine. The second and third surveys were made in 1953 and 1957 41bid. 51953 Adrian Lake Survey, Institute For Fisheries Research, Michigan Department of Conservation. 14 by C. M. Taube and include net-survey data. To provide current informa- tion on Adrian Lake fishes, a seining and gill-net survey was made on June 14 and 30, 1965. Survey effort consisted of approximately fifteen pulls of a lOO-foot seine at various places along the shoreline and four hours of fishing with an 80 foot 1 l/2-inch mesh gill net. The results of the 1965 survey are given in Table 1. A comparison of species composition for all four surveys is given in Table 2. Information on fishes in the 1946 survey was limited to the personal knowledge of Messrs. Smith, Peters, and Munger of the Adrian City Water Board. The abundance designations assigned to the various species in the 1953 and 1957 Surveys are those of Taube, and the criteria for assigning these designations are unknown. The 1965 data are expressed as numbers caught, except in the case of certain minnows, because survey effort was not geared to suggest estimates of abundance. Stocking effort. Table 3 summarizes the official stocking history of Adrian Lake as obtained from the records of the Michigan Department of Conservation. Population dynamics. The limited data of Table 2 seem to indicate that species composition is relatively stable and has been so since at least 1953. All but two of the species recorded in 1953 were found to be present in 1965. In addition the 1965 survey showed the presence of one heretofore unreported species, the mottled sculpin. Insufficient information exists to conjecture on growth rates of the black basses and northern pike. However, the growth rate of sunfishes is apparently poor. In both 19536 and 19577, Taube reported the dominant 6Ibid. 71957 Adrian Lake Survey, Institute For Fisheries Research, Michigan Department of Conservation. 15 .mchm wsu Eouw vmmmomw xHUmumwmmu LUHLB Lme LocHunH mHmumaonuma< ax ucmmmua wwa mmboE bmchmb prmeo 038 « n m.m um.q m o AHHmsoquv memomm>mHm mopmm Loumm 3oHHm% u n n H msvmmchmm Esanc mEOumooLum pmuumb hence“ a n n H AvumuHUv mumHsomE mcHupwm kuumv mvaxoch mo u u u H vumuHo Hquwn msuuov :HmHsom UoHuuoE .c musm ~55 ohm mcHLmHm umc HHHw mo muses “now new mHHom mchm :mmuwHw AkumEonumm< .Umuammmumwu .moaH .om new «H mesh :0 wmuusvcoo mm>usm um: HHHwowchHmm mme cmHuv< mnu mo muHSmmm .H mHQMH l6 msoumssc u s u umcHsm HkuuaoHHmBm msouwesc u ucmmoum n umcHSm GHH emu mDOHmBSC u u n umcHLm kumwummOH n ucmmmum ucmmwpm a pmcHLw oHEHE msoumEDC ucmmmum ucwmmum u umchm emnHow u n osmmwum a 30ccHE Ummzumm msoumasc ucmmwum ucmmmpa n capo xmmuo om u ucmmwum u umchm 005800 6 ucmbcsnm ucmwcsnm kuuommu mumo m50u0850 ucmmmum ucwmmua n BoccHE mmocucan muzm Loummmmx xuwsmHm Mom quuHumcH .mxmq :mHun4 c0 coHumBCOHCH coHumHnmom anw «0 coHummHumEESm .N anmH l7 ooo.H mwcaaummcuu mafia assesses Haas oem.H euwcma .m>m :o.m seam assesses smaa ado.“ auwcma .m>m =m.m amen LuzoaHHmEm seas UwHUOum HmnESZ Umxooum mNHm mmHowmw bmxooum umwM coHum>ummcou H0 ucweupmmma cmmHson wLu Eoum umCHMuno mm mme cmHuv< pow whoomu mcHxUOum .m magma .wnmom noun: qu0 :mHuU¢ mLu Ho Homes: new .mumuwm .cuHEm .mummwz mo mwvaBOCx HmCOmHmQ msu 00 bmuHEHH mma >m>usm oqu 050 CH meme co coHumEHOHCH a H unmmmum ucmmmua u uwuumu xccnOH H ucwmmum ucwmmua a Coupon mmexomHn 0 008800 coeaoo Uwuuoamu zoumm 30HHmm mHmQ< .Hu mustnH @ g 3:3 c384 333 ammwu :25 .8 $33 SH zofiafim A3333“ O . o a ...u.u.n.u.m% a O .m {4.0.1 .0 .m o .v . zv 1 Q l l l ‘ ‘ G . N . H P a o 0 “do: . U.. . Ego 9H» amen .HHH ZOHH0nnw QHHE one vHomHU 30.3 do no ZOHHoo ooH Hons .noHuodponudH HuOmSO .mmanomo spew ooHSHm o» GoHumHon aH HHH £355 as needs“ Hommoo H30» mo moHHHounH Houses.» me wGHumuumzHHH 8.9%me < .o oumeh .90 Ema mo . \_ \ r s j l m HV I. L m u w w v V W a 1 a. a. .m .m n m. m I Z I I 9 I R Z 6 .7 S H o 23.n— >m3H Human. — AonH>H _ wanedhnoh — innmddmh o H F pouHoE enemas. ao>oO 00H wcHBOHH «on HoemoHu HGHBOHH ”oumHHSm Ho. .00. demo " mooHaHm SD ~ sxeieux u; qidap 43 lake's cOpper profile. On April 1A a large density current was going over the dam (esti— mated 113 million gallons per day), and the copper sulfate had been shut off for eight days. In this instance the incoming stream picked up cop- per in Area A and transported it across the surface of the lake to pass over the dam. Here, however, the mechanism for picking up cOpper from the bottom.is uncertain. If it were current action picking up fine cop- per-bearing material, we would expect to find high sestonic copper values in the top water density current. However, sestonic copper values were actually relatively low and constant from surface to bottom, refuting the idea of physical suspension of particulate capper-bearing matter. These data indicate the copper was picked up in some other fashion. On April 29 the volume of water entering the lake was consider- ably less than on March 15 and April 1h, although the dam sluices were open and an estimated three million gallons of water per day was flowing over the dam. The copper sulfate was shut off. Dissolved oxygen concen- trations were constant from surface to bottom, and water transparency had increased significantly. Copper concentrations were nearly constant from surface to bottom. It appears that a prolonged gentle mixing of the lake was responsible for the homogenous concentrations. The May 12 sampling provided a definite contrast. The sluice gates were Open, the copper sulfate had been flowing for eight days, and no water was going over the dam. In this instance, copper concentrations 'were higher below 2.5 meters and increased progressively to the bottom, suggesting a density current. May 27 found the sluice gates closed, no overflow, and the copper sulfate flowing. About three million gallons of water per day were being 44 used by the water plant. Lake copper concentrations were relatively con- stant, although a slight, yet steady, increase with water depth was re- corded. Effect of Copper Sulfate on Lake Water Copper The introduction of copper sulfate to the lake via the constant- flow device had a definite effect on copper content at all parts of the lake, as long as a volume of water was passing through the lake. January 16, 30, and February 6, which exhibited discharge through the sluice gates and copper sulfate flowing, exhibited strikingly higher total copper values, ranging up to 0.177 ppm. on January 30. Further ex- amination of the data showed the filtrate fraction to be very high and the sestonic fraction to be relatively low, showing most of the total cop- per had gone from the copper sulfate pipe into substances such as soluble inorganic compounds or organic complexes. The applied copper was not pri- marily tied up with algae, detritus, or clay particles, or it would have shown up in the sestonic fraction. A shut down of the copper sulfate flow caused a marked decrease in the total copper content and a marked increase in the proportion of sestonic copper. Under this condition, total copper was primarily ses- tonic in nature on March 15, April 14, and April 29. The inflowing fil- trate fraction, losing the source of constantly-fed copper-ions by the shut down, simply remained minute. The form(s) the sestonic fraction took are unknown. However, the lake was relatively turbid on all three of the above dates. The constant-flow copper sulfate operation was re-continued on May 4. However, the sluice gates were closed on May 12 and no water traveled over the dam. The only draw on the lake was caused by the 45 approximate three million gallons per day consumed by the water plant. With no significant current to bring the applied copper down the lake, total copper concentrations increased slightly, but not nearly to the ex- tent of the January 16 through February 6 period. It is assumed that the introduced copper remained at the upper end of the lake during the May sampling period. The form of the copper at this time can only be conjectured. Several alternatives as to what happens as the copper ions leave the constant-feed pipe include: (1) an accumulation of copper ions in solution; (2) formation of a soluble cop- per compound(s); (3) deposition as an insoluble copper compound, and (4) precipitation through adsorption to clay particles and/or other colloidal material. Alternative (1) is very unlikely, because of the alkaline character of the inflowing water. The remaining three are all possible and probable. A pile of flocculent material completely covers the constant- flow pipe in the inlet stream each summer. The accumulated material ex- hibits a bright greenish-blue color on the downstream side, the color of which is doubtless due to an inorganic copper compound, possibly the car- bonate. Sediment Core 2 was taken from the center of this pile of floc. The frozen 85-cm. long core exhibited numerous layers of the greenish- blue precipitate, while interim sediment layers were brown silty-clay. At least some of the copper ions passing from the pipe through the floc pile are reacting with components of the lake water. It is also possible that erosional destruction of this pile during periods of high water con- tributes greatly to the sestonic copper fraction of the lake at these times. 46 Estimated Amount of Copper Carried Out of The Lake A prime objective of the study was to estimate the amount of ap- plied copper which was carried out of the lake during the spring runoff. This was done to determine if Such loss is actually a substantial amount. The period surveyed for copper loss was April 14 through June 4. Table 4 summarizes the computations and gives the various estimates of copper inflow and loss. An estimated 153 pounds of natural copper was carried into Adrian Lake by the Wolf Creek during the survey period. An estimated total of 253 pounds was carried out, theoretically including 105 pounds of previously applied copper. This estimate is at best crude. However, it does give dimension to the fact that a significant amount of copper is transported from the system via high water conditions. Of special significance is the fact that the greatest amount was carried out over the dam during high water conditions at a time when the copper sulfate was not being, and had not been, fed into the lake. This was copper picked up from the sediment, as indicated by the March 15 data. The total copper values measured on January 16, January 30, and February 6 at Station III were very high, ranging from 0.067 ppm. to 0.177 ppm. As mentioned before, these high values Were due to the fact that the copper sulfate was flowing. It is apparent that any large vol- ume of water would carry these copper-rich waters through and out of the system. Although no discharge data are available, if a conservative sus- tained sluice gate discharge of twenty-eight acre feet of water per day containing 0.10 ppm. of copper is assumed, an estimated 230 pounds of cop- per would be carried out in a month as long as the copper sulfate flow was maintained. Since there is roughly twenty-five pounds of copper in 47 .AcoHudEsmcoo HmmHowcsa msHm owumsome Emp pom oumw moHsHmv masocomaoo Bon uso onu mo 83m emu Hmsvm tznsou cu nwasmmm mma aoncH oLH as .moumw ooHsHm emu mo xuwommmo onw nHst mucouuoco mcflpsmww .poucm>pm ma Amp pom mcoHHmm coHHHHE mm mo oumEHumm xumuuwnum :4 % o.¢oH pm>OEom mommoo pmHHdmm Ho deDOQ HmuOH m.mmH ome oLu OucH poHunmo pomdoo Ho mpc:0d HmuOH H.mmN ome oLu mo uno poHuumo ummdoo mo mUCSOd HmuoH m.mmH m.mH H.mm m.nm H.NN ome OucH voHpumo so .mnH Nasamo. ommaea. mmmmso. Nanoao. doom atom use so .maa ass. was. smo. aoo. A.saav senses am .500 so «.00N a.maq s.omm s.a~o.~ gazetted asst scum .smm mmflmz UZHSOAMZH H.pmm uso postmo so HmuoH o.oq m.NH n.mH m.o N.~ uso poHuumo .mbH .umo omoxoo. wmmqpo. oomoqo. oquwo. uoow meow cod no .mnH mmo. amo. has. Omo. A.Eaav sashes as .cou so m.OmH m.NOH m.qu «.mm mossmcoo meow ouom ZOHHAZszoo Hzo mux9o?e?e?e?e?e?e?e?e8.9.?090’09.90%...e$9.? ’.'............‘........ &&&&3”””’%”%&&&&&$ .O.O.OIO.O.O.O. .0... 2 W 4 m 4 555555:35555555555555: 6 W 6 35555555 8 8 .O.9.v.v.v.: m CORE 4 CORE 6 10 m 10 m 12 m 12 a 14 E 14 Q 1 6 a 5 O O 10 00 500 1000 10 depth in cm. of sample in core 12 CORE 10 CORE l4 l4 16 500 1000 500 1000 0 0 Z 2 4 4 6 6 8 8 CORE l6 CORE 17 10 10 12 Figure 7. Vertical profiles of total copper in mg. per kg. dry sediment from six Adrian Lake cores. 52 as 23, 53, 67 and 77 ppm. Assuming each core's lower copper values repre- sent applications of copper sulfate from the late 1940's and early 1950's, the 10 cm. depth probably represents the amount of sedimentation in Adrian Lake over this period. Cores 17, 21, 23, and 27, all of which were collected in Area C, did not observably follow the trend exhibited by the majority of cores. Instead, these cores tended to exhibit constant values from surface to base, as exemplified by core 17 in Figure 7. It should be noted that cores l7 and 23 were respectively collected from 5.8 and 5.5 meters of water and are the deepest two samples taken. Cores 21 and 27 also rank among the deeper samples. It is reasonable to assume that the rate of sedimentation is greater in the deeper waters, and that the frozen corer simply did not obtain sufficient length cores to expose the decreasing copper profile shown by the remainder of the cores. Copper concentration with respect to water dgpth. Nichols et a1. (1946) report higher values of total copper in the profundal regions of treated Wisconsin lakes. Riley (1939) mentions this phenomena, though not providing data on Lindsley Pond. The Adrian Lake data were examined to determine if higher concen- trations of copper existed in the deeper waters of the lake. A linear re- gression analysis was run upon data from the eighteen cores collected in Areas B and C, using depth of the sample as the independent variable and total copper concentration as the dependent variable. The correlation co- efficient was found to be 0.311 and a test of the hypothesis that the slope equals zero was found to lack significance at the 5 percent level (F 3 1.719 with 1 and 17 d.f.). Thus, the data provide no evidence of in- creasing copper concentration with increasing water depth in Adrian Lake. 53 Nichols et a1. felt the ”natural grading process”, wherein fine material is carried eventually to deeper water, is instrumental in achiev- ing higher copper values in the deeper sediments of the treated Madison Lakes. Since Adrian Lake data does not support such a relationship, there is either (1) a significant difference between the Madison Lakesand Adrian Lake in the ”natural grading process” or (2) the sample size col— lected at Adrian Lake is insufficient to portray copper concentration dif- ferences over the narrow depth range sampled. Although the sedimentation process will obviously be different between a small reservoir and large natural lakes, the latter explanation seems more plausible. Lake Menona has depths exceeding eighty feet, whereas Adrian Lake is not over twenty- five feet deep. The eighteen Adrian Lake cores compared were collected from 1.75 to 5.8 meter depths, which is a range of approximately twelve feet. In contrast, samples from Lake Menona were collected from a depth range over five times as great. Cppper concentration with respect to distance from the point of introduction. Since 71.3 percent of the 192,813 pounds of copper sulfate applied to Adrian Lake over the 1952-64 period were introduced by the con- stant-flow device, an excellent opportunity was afforded to analyze the importance of proximity to the point of introduction on copper accumula- tion in sediments. Theoretically, relatively fast precipitation of cop- per as insoluble inorganic salts and/or organic complexes, could result in very high copper concentrations in the upper end of the lake. The highest total copper values from all twenty-seven cores are shown plotted in Figure 8 arranged in order of distance from the constant-flow copper sulfate source. Although no regression analysis was done, it is evident 54 151, 000 ppm at pile of floc by CuSO4 pipe .- 03 O A .. O 3’02 H AREA A—un—AREA B AREA c-——-J> uplake midlake downlake A .0 0' '0 O 2000 O 02 ,. 02 A .v .. O A 9‘9' .7 .9 O A‘A '9' b? to J 1500 Total Cu (ppm) '5 o o 500 Native Stream Concentration Inlet : Upstream Dam Figure 8. A graphic presentation of Adrian Lake sediment core copper concentration with respect to distance from the point of copper sulfate introduction. that these data indicate no very strong relationship between copper con- centration and distance from copper source. Actually, little supporting evidence even exists, which might sup- port such a permanent trend in Adrian Lake. Distribution of applied cop- per at the lake inlet and in Area A is obviously static. Despite the fact that becalmed and low-inflow conditions result in copper compound accumulations at the inlet, wave action and intensified inflow, whenever they might occur, result in full or partial re-distribution of these com- pounds. This re-distribution is of course ultimately down-lake. Support- ing evidence of ”re-distribution” by currents is provided by the March 15 water sampling data. l. SUlflflARY A study was made of the dynamics of movement and accumulation of ap- plied copper in Adrian Lake, an 85-acre southeastern Michigan hard- water water supply impoundment. The lake has accrued a copper accu- mulation during more than ten years of intensive algal control with cepper sulfate by the City of Adrian. Applications occurred as early as 1946. Available records show that from 1951-64, 192,818 pounds of commercial grade copper sulfate were applied, and approximately 70 percent of the total entered through a continually operating constant- feed device located at the lake inlet. The study extended over the period January through May, 1965. Spe- cific objectives were: (a) to evaluate the accumulated copper dis- tribution in the sediments with respect to water depth and distance from the point of constant-feed copper sulfate introduction; and (b) to evaluate vertical and horizontal copper profiles of lake water with respect to how they affect the movement and distribution of applied copper in Adrian Lake. During the study Adrian Lake water dynamics were found to be con- stantly changing. Under-ice dissolved oxygen profiles showed a gentle progression towards stratification. A snow-melt and rainy period in early February resulted in a thorough under-ice lake mix- ture. Open-water sampling from April 13 through May 27 showed a gradual progressive development to stratification after the overturn. Dissolved oxygen values below 1.0 ppm. were found at the deeper levels during the latter half of May. 56 57 An evaluation of water copper profiles for the eight sampling dates resulted in the conclusion that water movement is a very significant factor in the movement of applied copper through and out of Adrian Lake. The measured copper profile dynamics can be largely explained by the degree of water movement. Factors apparently most important in the mechanism are: (a) volume of lake inflow; (b) presence, or lack, of copper sulfate entering the system; and (c) water volume go- ing over the dam and/or through the sluices. On March 15 a strong density current was traversing the sub- merged WOlf Creek stream channel to pass out through the dam sluices. Copper sulfate constant-feed was shut down and the residual or stag- nant water layer above the density flow maintained relatively high copper values from some prior currentless period, when the copper sulfate was flowing. With no artificial source of copper the dilute density current exhibited low natural copper values with the excep- tion of the bottom one and one-half meters. Examination of the ses- tonic copper profiles indicated that the density current was sweep- ing copper-bearing particulate matter into the seston from the bottom. Introduction of copper sulfate via the constant-flow device had a definite effect on lake water copper content at all parts of the lake, as long as a volume of water was traversing the lake. With cop- per sulfate flowing and a sluice gate discharge, the proportion of filtrate copper soared and the sestonic fractions were low, indicating most applied copper had combined into soluble substances. With low inflow and no water going out the dam, and thus no current to bring the copper down lake, the data indicate that the introduced copper remained at the upper end of the lake. The forms are assumed to be Sd deposited insoluble copper compounds and/or copper-colloidal material complexes. During the period April 14 - June 4 an estimated 105 pounds of applied copper was transported out of Adrian Lake. A crude estimate at best, this statistic does give dimension to the fact that a sig- nificant amount of copper is carried from the system via high water conditions. Of Special significance is the fact that the greatest amount of the estinate was transported out at a time when copper sul- fate was not being, and had not been for some time, fed into the lake. Copper is tranSported out of Adrian Lake both by direct flow from the constant-flow source and by carrying it from the sediments. In each instance water currents are the vehicle which determines the rate of removal. Total copper values in the sediments were found to be high, but not nearly as high as anticipated. A maximum down lake value of 1,982 ppm. was found two cm. deep in Core 5, 1,145 feet from the point of copper sulfate introduction. A specific trend was found in the vertical distribution of cop- per in the cores. Copper content prOgressively decreased with in- creasing sediment depth. The available records show that annual cop- per sulfate applications have generally increased since 1951, and the vertical trend apparently reflects the lake's rate of copper sulfate application. It seems that when more copper is applied, more is in- corporated into the sediments. Assuming each core's lower copper values represent applications of copper sulfate from the late 1940's and early 1950's, the 10 cm. depth probably represents the approxi- mate depth of sedimentation in Adrian Lake over this period. S9 The data provide no evidence of increasing sediment copper con- centration with increasing water depth in Adrian Lake. However, it was concluded that the sample size was insufficient to portray copper concentration differences over the narrow depth range sampled (lZ-feet). Nor does data provide evidence of a strong relationship between sediment copper concentration and distance down lake from the constant- flow copper sulfate device. Little evidence even exists, which might support such a permanent trend at Adrian Lake, since the water sampl- ing showed the distribution of applied copper at the lake inlet is static. Wave action and intensified inflow, whenever they might occur, are attributed to result in continual full or partial down lake re-dis- tribution of these compounds. The literature review resulted in the conclusion that the important high affinity of organic matter for copper ions has been generally unrecognized in the field of lake copper ecology. A thorough under- standing of copper ion reactions in natural waters is precluded until such time as a more ample background is established on form of copper ions in the water, the organic and inorganic materials present, their inter-relationships, and relative copper affinities. A review of the existing fish population records and a cursory seine— gill net survey was done. The limited data seem to indicate that spe- cies composition has remained relatively stable since at least 1953. All but two of the species recorded in 1953 were found to be present in 1965. In addition the 1965 survey showed the presence of one here- tofore unreported clean-water species, the mottled sculpin. Sunfish growth has traditionally remained poor. LITERATURE CITED A. P. H. A., A. W. W. A. and W. P. C. F. 1960. Standard methods for the examination of water and wastewater. Eleventh edition. Bartholomew, K. A. 1953. Control of earthy, musty odors in water by treat- ment with residual copper. A.W.W.A.J. 50:481-436. Benoit, R. J. 1956. Studies on the biogeochemistry of cobalt and related elements. Ph.D. Dissertation, Yale University. Borchardt, L. G. and J. P. Butler. 1957. Determination of trace amounts of copper. Anal. Chem. 29:414. Bremmer, J. M., P. J. Mann, 5. G. Feintze and H. Lees. 1946. Metallo- organic complexes in the soil. Nature 158:790-791. Broadbent, F. E. 1955. Basic problems in organic matter transformations. Soil Sci. 79:107-114. Broadbent, F. E. and J. B. 0h. 1957. Soil organic matter-metal complexes: 1. Soil Sci. 83:419-427. Brown, E. H. 1964. Fish activation with copper sulfate in relation to fyke-netting and angling. Pub. W-7l. Ohio Division of Wildlife. Coleman, N. T., A. C. McClung and D. P. Moore. 1956. Formation con- stants for Cu (11) - peat complexes. Sci. 123:330-331. Corwin, A. H. 1950. The formation of copper complexes. IniA symposium on copper metabolism. Baltimore. The Johns Hopkins Press. Domogalla, B. 1935. Eleven years of chemical treatment of the Madison lakes - its effects on fish and fish food. Trans. Am. Fish Soc. 65:115-120. Fogg, G. E. and D. F. Westlake. 1955. The importance of extracellular products of algaes in fresh water. Verh. int. Ver. Limno. 12:219-232. Frey, D. G. 1940. Growth and ecology of the carp, Cyprinus carpio Linnaeus, in four lakes of the Madison Region, Wisconsin. Ph.D. Dissertation. University of Wisconsin. Hale, F. E. 1954. The use of copper sulfate in control of microscopic organisms. Phelps-Dodge Refining Corp. New York, N. Y. 44p. Nasler, A. D. 1947. Antibiotic aSpects of c0pper treatment of lakes. Wis. Acad. Sci. Arts & Letters. 39297-103. 60 61 Hutchinson, G. E. 1957. A treatise on limnolOgy. Vol. 1. GeOgraphy, physics, and chemistry. N. Y. Wiley and Sons, Inc. 1015 pp. Klein, L. 1957. Aspects of river pollution. N. Y. Academic Press, Inc. Publishers. Mackenthun, K. M. and H. L. Cooley. 1952. The biological effect of cop- per sulfate treatment on lake ecology. lrans. Wis. Acad. Sci. Arts & Letters. 41:177-187. Moyle, J. B. 1949. The use of copper sulfate for algal control and its biological implications. In: LimnolOgical aspects of water supply and waste disposal. Am. Asso. Adv. Sci., 87 pp. Nichols, M. S., T. Henkel, and D. McNall. 1946. Copper in lake muds from lakes of the Madison area. Trans. Wis. Acad. Sci. Arts & Letters. 38:333-350. Ohlmacher, F. J. 1964. A coring device for freezing samples of lake sediments. M. S. Thesis. Central Michigan University. Placak, O. R., nuchhoft, C. C., and Snapp, R. G. 1950. Copper and chromate ions in sewage dilutions. Industr. Engng. Chem. 41:2238-41. Prescott, G. W. 1943. Objectionable algae with reference to the killing of fish and other animals. HydrobiolOgia l (1): 1-13. Prytherch, F. F. 1934. The role of copper in the settling, metamorphas- is, and distribution of the American oySter, Ostrea virginica. Ecol. Monographs. 4(1):47-107. Riley, G. A. 1939. Limnological studies in Connecticut. Ecol. Mono- graphs 9:53-94. Rudgal, H. T., 1946. Copper in sludge digestion: effect of copper on the operation of the Kenosha plant. Water and Sewage Works. 93:316. Saunders, G. W. 1957. Interrelationships of dissolved organic matter and phytoplankton. Bot. Rev. 23:399. Shapiro, J. 1957. Chemical and biological studies on the yellow organic acids of lakewater. Limno. and OceanOgr. 2:161-179. Smith, G. F. 1954. The trace element determination of copper and mercury in pulp and paper. G. F. Smith Chem. Co., Columbus, Ohio. Striker, M. M. and L. I. Harmon. 1961. Soil Survey of Lenawee County, Michigan. 1947 Series (10). U. S. Dept. of Ag. and Mich. Ag. Ex. Sta. Thompson, J. B. 1950. A browning reaction involving c0pper-proteins. In: A symposium on copper metabolism. Baltimore. The Johns Hopkins Press. 62 Tompkins, W. A. and C. Bridges. 1958. The use of copper sulfate to in- crease fyke-net catches. Prog. Fish Cul. Jan. 1958:16-20. Vallentyne, J. R. 1957. The molecular nature of organic matter in lakes and oceans, with lesser reference to sewage and terrestrial soils. J. Fish Res. Ed. Canada. 14:33-82. 63 .uw ens“ wcficcsu uHmE 305m Luw3 maoz mow Eonw cmxmu mmHmEmm « 0.0 N.0 m.0 0.0 m.m 0.0 m.m 0.0 0.n H.HH m.m m.0 m.m 0.0 0.0 0.NH 0 0.0 m.0 m.m «.m m.~ H.0 m.m N.0 0.0 0.HH m.u «.0 m.n 0.0 0.0 0.NH m 0.m m.0 0.0 «.m m.~ 0.0a m.m 0.0 0.0 H.HH m.~ «.0H m.n N.0H 0.0 m.NH « 0.0 «.m m.“ 0.0 m.m N.0H m.m 0.0 0.0 m.HH m.n 0.0H m.“ N.NH 0.0 0.NH m 0.0 m.m m.m 0.0H m.m m.0H m.m N.0 0.0 0.0H m.m N.HH m.m «.NH 0.0 0.0a N 0.0 H.0 m.m 0.0a m.m m.0H m.“ N.0 0.0 «.HH m.m 0.0a m.n N.NH 0.0 n H 0.0 H.0 m.m 0.HH m.“ m.0H m.m N.0 0.0 0.0H 0.0 «.NH m.m a 0.0 u mumume 0 HHH cowumum 0.0 0.m m.n «.0 m.u 0.0a m.m «.0 0.0 «.HH m.n «.0 m.m N.0 n n « 0.0 «.0 m.m 0.0 m.n N.0H m.m 0.0 0.0 «.HH m.~ «.0H m.n «.NH n n m 0.0 m.m m.0 0.0H m.m N.0H m.~ «.0 0.0 N.Ha m.m N.NH m.m N.NH u u N 0.0 N.m m.m 0.0a m.m m.0H m.n «.0 0.0 0.0a «0.0 N.NH m.n «.NH n a H 0.0 «.0 m.m 0.0a m.n N.0H m.m «.0 0.0 «.0H «m.0 m.mH u u n u mnmuma 0 E SEEM 2% .05 em .00 54% .05 :m .05 mm .05 :0 .05 :m .06 mm .00 IMMIEAI S .3: 2 £3 3 d3. 2 .32 0 .ad cm .56 2.5:. m00a .oxmq cmfiup< um popuoomu mosam> m0 0cm swwxxo po>H0mmHQ .H xfipcm00¢ 64 Appendix 2. Alkalinity values recorded from Adrian Lake, 1965 Depth Sample Collected 2 meters 5 meters Date Carbonates Bicarbonates Carbonates Bicarbonates January 30 0 ppm. 136 ppm. 0 ppm. 228 ppm. February 6 0 ppm. 194 ppm. 0 ppm. 214 ppm. nmrch 15 0 ppm. 102 ppm. 0 ppm. 125 ppm. April 29 0 ppm. 178 ppm. 0 ppm. 182 ppm. day 27 0 ppm. 189 ppm. 0 ppm. 212 ppm. 65 - - - - - - - - - o.o >H zoneaem - - - Boo. moo. moo. - - mao. o.o oko. sacs emo. umoa umoa umoH - - oHH. m.m coo. ado. Mao. emo. moo. meo. - - mNH. o.m moo. Nao. “so. amen “mos umoa - - moo. m.e umoa ado. ssh. meo. ooo. mso. - - oao. o.e omoH moo. ooo. “mo. moo. aeo. - - - m.m moo. oao. aao. meo. Boo. omo. - - moo. o.o oao. mao. Noa. «no. moo. ado. - - AAA. o.N oeo. oHo. nmo. moo. moo. omo. - - ooa. o.H emo. Hmo. wmo. - - - - - - o.o HHH oneaem - - - amo. ooo. oeo. - - - m.e omo. mmo. mmo. soo. soo. moo. - - - o.o Koo. mmo. moH. Aoo. ooo. oao. - - - m.m «as. moo. oao. omo. Hoo. moo. - - - o.m moo. ooo. oeo. - - - - - - m.~ moo. mao. omo. Nmo. aao. ooo. - - - o.~ “so. koo. mmo. umOa smog omen - - - o.H ANo. Mao. “mo. - - - - - - o.o HH zoaeaem mea. Nmo. Nam. - - - - - - o.H H onHaem mea. «mo. “an. - - - - - - Nmo. Hmo. ado. - - - - - - o.H o zoneaem o-o .umwm Hence o-o .ummm Hence o-o .ummm sauce A.av cameo 0 mumnunmm om humsamh 0H humscmh wouHH\we mm nmmmmwdxm 30v m00a .wxmq cmflup< um popuoomu monam> ummdoo umumsoxmq .Aumum3ome mo .m xquwamfi 66 - mNo. NHo. AHo. moo. mmo. - - - o.o >H onoaem - two. mao. - - - mao. mmo. Hmo. o.o - - - - - - mao. omo. oNo. m.m - oNo. oao. - - - mao. meo. Nao. o.m - - - - - - mao. oNo. aoo. m.e - oNo. Ado. - - - oao. moo. ooo. o.o - - - - - - oao. «No. Nao. m.m - oNo. oao. - - - mao. Ado. oHo. o.o - Hmo. Nmo. - - - oao. mmo. «No. o.o - amo. «No. - - - emo. «mo. meo. o.H - amo. omo. - - - amo. aeo. oso. o.o HHH oneaem - - - - - - HNo. ado. mmo. m.s - mNo. omo. - - - HNo. oso. weo. o.e - - - - - - oNo. qso. mao. m.m - mNo. oso. - - - moo. Neo. oHo. o.m - - - - - - mao. meo. Hmo. m.~ - oNo. mNo. - - - amen Nmo. omo. o.~ - amo. Nmo. - - - aNo. soo. omo. o.H - woo. ado. - - - mmo. omo. mao. o.o HH onHaHm - oeo. moo. - - - mao. oso. sNo. o.H H onaahm - Nao. soo. soo. moo. mao. oao. mmo. Mao. o.a o oneaem o-o .ummm sauce o-o .ummm swoop o-o .ummm Mason new gamma «a flange o aataa ma eons: goodwucouv .0 63950an 67 - mao. omo. o omo. omo. mHo. omo. o.o >H onHaHm - amo. Hmo. - mNo. Neo. omo. oHo. o.o - - - - - - - - m.m - omo. Nmo. - aHo. omo. oHo. HNo. o.m - - - - - - - - m.a - amo. omo. - mmo. amo. NHo. oHo. o.e - - - - - - - - m.m - «Ho. Amo. - moo. amo. moo. oHo. o.o - mHo. NNo. - ooo. emo. oHo. oNo. o.N - omo. oHo. - moo. mNo. NHo. HNo. o.H - AHo. mmo. - Hao. Hmo. mHo. AHo. o.o HHH onHaem I I I I I I I I moq - emo. amo. - «mo. omo. HNo. mmo. o.o - - - - - - - - m.m - oNo. amo. - oeo. Hoo. mHo. mNo. o.o - - - - - - - - m.N - oNo. emo. - ooo. moo. oHo. mHo. o.N - mmo. Hmo. - oHo. Nmo. mHo. oHo. o.a - oao. mNo. - oHo. omo. HNo. Amo. o.o HH oneaem - ooo. omo. - omo. moo. moo. omo. o.H H onHaem - mHo. aHo. - oao. Nao. mHo. Amo. o.H o onHaHm o-o .ummm. Hmsoa o.o .umam Hosea o-o .uwmm Hence “.50 gamma mmlwdz NH mm: 0N HHHNQ, .Hs.::aucooo .m prcwda< 68 Appendix 4. Sediment core copper values recorded at Adrian Lake, 1965 (Cu expressed as mg/kg dry sediment). Core No. l 2 3 Water depth (m.) 0.3 0.3 0.3 cm. down from mud-water interface Total Cu in mg/kg dry sediment O 16 151,571 176 5 33 22,566 121 - 10 13 32,391 139 15 8 34,465 5 20 11 31,225 56 25 12 13,081 33 30 33 24,542 21 35 - 29,610 13 40 - 14,382 - 45 — 17,406 63 50 - 37,471 14 55 - 138,208 17 60 - 144,897 33 65 - 646 - 70 - 423 - 7S - 73 - 80 - 193 - 85 - 732 - 69 - - - - - one - - - - - AHH oH oem - - - - omm - - - - - mm oH mmH NHH - - - mam - - - oHH - ea eH mom NeH - - - amo - - - mm - oma NH Nan Nam - - - sow Nam - mamm.H mma Now as oa ”Ho NHN mas Nan - too.H mam No HaN.H Nam mma mmm o “no NNm mom sow - NoN.H moo mom omo.H eHm mma Now o mos ass mom aeo was moo mom Ham moa.H Hmo oos.H Ham a mmo.a awe ohm one mas «Hm.H NNH.H mHo emu.H mam Nom.H sow N max Nos ado mam was was dam oHe was was ass Ame o ucaanmm Naplflmee CH :0 Hmuow wommwmucH pmumBIpsE Eoum c300 .Eo m.m o.N o.o a.N a.H a.m e.a a.o m.H A.o m.o s.o A.ev enema mama mH as MH NH AH oH a m A o m a .02 mtoo . .AvoscHucoov « prcmadd 70 0H - - - - - - - - oH - - - - - - - - sH - - - - Nam - oNo - NH - NN - sen mme - ooa son oH omm Noe omN moo mom - MHo Non o MN N ooN a Nam a moo aNa - mHo «on o do n HHm NNN oN Nam moH.H 0N saN HNo a Na mmH N omm mHo on How sea NNo NNo mow N eaN Nos H moN sNa emm oom omm one mam mmN o ucmEHpmmeupiwx\mE CH :0 Hmuoa mommumucH umumBupse Eouw 6300 w.m o.m m.e m.m m.s N.m o.m m.« A.eo spams seed NN mN sN MN oN oH NH oH .oz.muoo .ApmacHucouv « prcmdm¢